Process for preparing (2-oxo-3-bornylidene/methyl)-benzene sulfonic acids

ABSTRACT

An anti-solar cosmetic composition contains as the anti-solar agent a compound of the formula ##STR1## wherein R represents a member selected from the group consisting of hydrogen, a halogen selected from the group consisting of chlorine and fluorine and alkyl containing 1-4 carbon atoms; R&#39; and R&#34; each independently represent a member selected from the group consisting of hydrogen and SO 3  M wherein M represents a member selected from the group consisting of hydrogen, organic ammonium group and a metal, wherein at least one of R&#39; and R&#34; is other than hydrogen, and R&#34; is a substituent at the para or meta position relative to the bornylidene ring. The anti-solar agent is present in amounts of 0.5-10 percent by weight of said composition.

This is a divisional (Rule 60) of Ser. No. 497,469 filed Aug. 14, 1974,now U.S. Pat. No. 4,165,336. Ser. No. 497,469 is in turn acontinuation-in-part of Ser. No. 440,570 filed Feb. 7, 1974, nowabandoned, which was relied upon and expressly incorporated by referenceinto Ser. No. 497,469.

The invention relates to new compounds capable not only of absorbingultra-violet rays of a specific range but also of exhibiting a broadrange of solubility in certain solvents or mixtures of solvents. Thus,the novel compounds of the present invention can be incorporated incosmetic compositions either as an active component, especially when thecomposition is to be used to protect human skin from harmful effects ofactinic rays, or as a preservative for cosmetic preparations susceptibleto degradation or discloloration by exposure to light waves.

It is known, for instance, that sunburn, or erythema, results from theexcessive exposure to human skin to the rays of the sun and the wavelengths of light in the range of 280-315 millimicrons, often called the"erythematous zone", are those which produce such sunburn. Below thiswave length range then sun rays do not present any particular danger,for they are filtered by the ozone in the atmosphere. However, the UVrays which are responsible for or which produce a desirable suntan arethose in the zone ranging from 315 to 400 millimicrons.

Consequently, if one desires to be exposed to solar radiation, it isimportant that the skin be protected with the aid of a compositioncontaining a substance which absorbs the UV rays in the erythematouszone, thereby avoiding an undesirable sunburn, which composition howeveralso transmits those wave lengths in the range of 315 to 400millimicrons so as to obtain a desirable suntan. In particular, it isnecessary to transmit those rays of wave lengths in the neighborhood of340 millimicrons, which impart maximum browning of the skin withouterythema.

Thus, the protective agent must exhibit a high absorbency power between280-315 millimicrons, and a weak absorbency power above 315millimicrons. In addition to this critical absorbing power, theprotective agent must have other properties and in particular it shouldexhibit good resistance to the exterior elements, that is, exhibit goodphotochemical stability, good thermal stability, and have sufficientaffinity for the skin and sufficient chemical stability so as not to beremoved or degraded by perspiration or at least by washing.

Further, it is also known that certain components and particularlycertain dyes often contained in various cosmetic preparations do notalways possess sufficient stability to light. These cosmeticcompositions are often provided in the form of a solution, emulsion,gel, suspension, aerosol or dispersion, packaged in clear glass ortransparent plastic containers and thus can be exposed to light rays notonly during use but also during storage. To protect these dyes there isgenerally incorporated into the preparation containing the same a"protective filter", or a compound capable of filtering light rays, asdisclosed, for instance, in French Pat. No. 2,004,142. However, suchprotective filters often exhibit insufficient solubility in thosesolvents or cosmetic bases most often employed and thus their use hasbeen considerably limited.

It has also been observed that some essentially colorless cosmeticcompositions, for example, colorless nail enamels frequently experiencesome alteration and turn yellow after prolonged exposure to light.

Thus it has been found that such cosmetic compositions, colored orcolorless, can be preserved in storage only for a certain limited periodof time, generally in the order only of a few weeks. To overcome thesedisadvantages, it has been proposed to incorporate in these compositionsa compound capable of filtering light rays. Such a compound, however,must not only exhibit good filtering characteristics, but also goodstability and a sufficient degree of solubility in the vehiclesconventionally employed in these cosmetic compositions. The presentinvention now provides new compounds having these different criteriawhich effectively overcome the disadvantages noted above.

Thus it is an object of the present invention to provide a compound ofthe formula ##STR2## wherein R represents a member selected from thegroup consisting of hydrogen; halogen such as Cl or F; and alkylcontaining 1-4 carbon atoms; R' and R" each independently represent amember selected from the group consisting of hydrogen and SO₃ M whereinM represents a member selected from the group consisting of hydrogen,organic ammonium group and a metal, at least one of R' and R" beingother than hydrogen, and R" is a substituent at the para or metaposition relative to the bornylidene ring.

The compounds of formula (I) wherein R" is SO₃ M are prepared byreacting a compound of the formula ##STR3## wherein R and R' have themeanings given above with concentrated sulfuric acid, or oleum orchlorosulfonic acid.

The compounds of formula (II) in turn can be prepared according to theHaller method which consists in condensing an aromatic aldehyde on thesodium salt of camphor, the latter being prepared by reacting camphorwith sodium or a strong base such as sodium amide, sodium hydride or asodium alcoholate. The reaction to produce compounds of formula (II) ispreferably performed in an inert solvent such as benzene, toluene orether, and there are selected as the initial reactants an aldehyde and acamphor derivative suitable for obtaining the desired compound.

It is also an object of the invention to provide compounds of formula(II) in which R' represents SO₃ M or when R' represents hydrogen Rrepresents a member selected from the group of fluorine and alkylcontaining 2-4 carbon atoms.

The metallic and ammonium salts of formula (I), i.e., the compounds forwhich R' and/or R" have the value SO₃ M, wherein M is other thanhydrogen can be isolated directly from the reaction medium by treatmentwith an inorganic base or with a metallic salt such as a sulfate orchloride. These metallic salts can also be obtained easily according tothe usual processes by neutralization of the corresponding sulfonic acidwith an inorganic base such as a hydroxide, a carbonate or a metallicalcoholate, or alternatively with an organic base such as a primary,secondary or tertiary amine, a quaternary ammonium hydroxide, or anamino acid with a basic character.

Finally, the ammonium salts of formula (I) can also be prepared bycation exchange between a quaternary ammonium halide and thecorresponding sulfonic acid of formula (I) which can, if desired, beemployed in the form of its sodium salt.

Representative metallic salts of sulfonic acids of formula (I) include,for instance, the sodium, potassium, lithium, calcium, magnesium andzinc salts. Representative organic bases that can be used to prepare anorganic ammonium salt of formula (I) include, for instance,monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, triisopropanolamine, lysineand arginine.

Representative compounds of the present invention include, for instance:

(1) 4-(2-oxo-3-bornylidene methyl) benzene sulfonic acid,

(2) sodium 4-(2-oxo-3-bornylidene methyl) benzene sulfonate,

(3) magnesium 4-(2-oxo-3-bornylidene methyl) benzene sulfonate,

(4) calcium 4-(2-oxo-3-bornylidene methyl) benzene sulfonate,

(5) 4-(2-oxo-3-bornylidene methyl) benzene sulfonate of bis(2-hydroxyethyl) ammonium,

(6) 4-(2-oxo-3-bornylidene methyl) benzene sulfonate of(1,3-dihydroxy-2-methyl-2-propyl) ammonium,

(7) 2-methyl-5-(2-oxo-3-bornylidene methyl) benzene sulfonic acid,

(8) potassium salt of 2-methyl-5-(2-oxo-3-bornylidene methyl) benzenesulfonic acid,

(9) sodium 2-methyl-5-(2-oxo-3-bornylidene methyl) benzene sulfonicacid,

(10) 4-(2-oxo-3-bornylidene methyl) benzene sulfonate of5-amino-5-carboxy pentylammonium,

(11) 2-chloro-5-(2-oxo-3-bornylidene methyl) benzene sulfonic acid,

(12) sodium 2-chloro-5-(2-oxo-3-bornylidene methyl) benzene sulfonicacid,

(13) 2-chloro-5-(2-oxo-3-bornylidene methyl) benzene sulfonate oftris-(2-hydroxy ethyl) ammonium,

(14) 3-benzylidene-2-oxo-10-bornane sulfonic acid,

(15) sodium 3-benzylidene-2-oxo-10-bornane sulfonic acid,

(16) 2-chloro-5-(2-oxo-3-bornylidene methyl) benzene sulfonate oftetradecyl trimethylammonium,

(17) 4-(2-oxo-3-bornylidene methyl) benzene sulfonate of benzyl dimethylhexadecylammonium,

(18) 2-methyl-5-(2-oxo-3-bornylidene methyl) benzene sulfonate ofdodecyl pyridinium,

(19) 4-(2-oxo-3-bornylidene methyl) benzene sulfonate of4-amino-4-carboxy butyl guanidinium and

(20) 2-methyl-5-(2-oxo-3-bornylidene methyl) benzene sulfonate of(1-hydroxy-2-methyl-2-propyl) ammonium.

The compounds of formula (I) exhibit like 3-benzylidene camphor and3-(4-methyl benzylidene) camphor designated respectively as compoundsIII and IV, the property of providing remarkable protection to the humanskin in the erythematous zone, i.e., in the range of wave lengths of 280to 315 millimicrons, while at the same time allowing the passage oflight rays of wave lengths greater than 315-320 millimicrons, thusproviding selective protection as it appears in the attached figure. Thecompounds of the present invention offer the considerable advantage ofhaving solubility properties that are clearly improved relative tocompounds III and IV mentioned above, particularly in aqueous solutionsin which these latter are insoluble, in hydroalcoholic solutions and inethanol.

The attached FIGURE, in which the abscissa indicates the wave lengths inmillimicrons and the ordinate indicates the transmission, in percentageof radiations considered, represents the transmission curves 2, 9, 15,III and IV of the following compounds dissolved at a rate of 0.08millimoles of active product in ethanol:

Compound 2: sodium 4-(2-oxo-4-bornylidene methyl) benzene sulfonate,

Compound 9: sodium salt of 2-methyl-5-(2-oxo bornylidene methyl) benzenesulfonic acid,

Compound 15: sodium salt of 3-benzylidene-2-oxo-10-bornane sulfonicacid,

Compound III: 3-benzylidene camphor and

Compound IV: 3-(4-methyl benzylidene) camphor.

It can be clearly seen that the curves relative to compounds 2, 9 and 15broadly cover the zone of 280 to 315 millimicrons.

Solubilities were determined in grams of product in 100 ml of solventrepresented by water, ethanol and a 50:50 water-ethanol solution forcompounds 1 to 7, 9, 14 and 20, and for 3-benzylidene camphor and3-(4-methyl benzylidene) camphor, designated respectively as III and IV.The following table indicates the results obtained.

    ______________________________________                                                                       Water-Ethanol                                  Compound  Water     Ethanol    (50:50)                                        ______________________________________                                        III       Insol.    14%        <0.5%                                          IV        Insol.    20%        <0.1%                                          1         100%      >100%      100%                                           2         5%        0.5%       14%                                            3         0.1%      20%        20%                                            4         0.2%      14%        10%                                            5         25%       25%        50%                                            6         17%       1%         33%                                            7         4%        50%        100%                                           9         10%       3%         25%                                            14        50%       100%       100%                                           20        50%       33%        50%                                            ______________________________________                                    

The association of the properties demonstrated by the transmissioncurve, on the one hand, and by the table of solubilities, on the other,makes it possible to appreciate in a particularly advantageous way theproblems and especially the limits of formulation imposed by the use ofcompounds III and IV, because of their insolubility in an aqueous andhydroalcoholic medium.

The present invention also has for an object a cosmetic composition,stable in regard to light radiations, thus assuring a protection in therange of wave lengths of 280 to 315 millimicrons, but selectivelypermitting the passage of rays above 315 millimicrons to obtain, underthe best conditions, a tanning free of erythema. This compositioncontains as the agent for protection from light radiations at least onecompound of the formula: ##STR4## wherein R, R' and R" have the meaningsgiven above.

This composition can be a solution in the form of a lotion, an emulsionin the form of a cream, gel, foam or milk, and generally in all theforms of the usual cosmetic compositions. The composition can alsocontain cosmetic adjuvants such as thickeners, softeners,superlubricants, emollients, wetting agents, surfactants, preservatives,antifoam agents, perfumes or any other compatible component usuallyemployed in cosmetics. Finally, the composition of this invention canalso contain one or more propellents and be packaged under pressure inan aerosol bomb or container.

The composition of the present invention contains 0.5 to 10% by weightof the compound of formula (I). Representative solvents that can be usedinclude water, lower mono- and polyalcohols and their mixtures or hydro-and oleo-alcoholic solutions. The alcohols employed are, preferably,ethanol, isopropyl alcohol, propyleneglycol, glycerol and sorbitol.Hydroalcoholic mixtures that can be used preferably are mixtures ofwater and ethyl alcohol wherein ethyl alcohol is present in amounts ofabout 10-70 percent by weight of said mixture.

The anti-solar composition can be either colorless or colored with dyesand/or pigments usually employed in such compositions, particularly,iron oxides in amounts of about 0.001% to 0.05% by weight of the totalweight of the composition.

The present invention also relates to a cosmetic composition whosecomponents are protected from light radiations by the presence of acompound of formula (I) present in an amount of 0.05 to 5% by weight,especially when the said composition contains one or more compoundsparticularly sensitive to ultraviolet rays. Representative of suchsensitive compounds are photosensitive dyes used in amounts of about0.001% to 0.05% of the total weight of the composition, andtriphenylmethane derivatives such as crystal violet, methyl violet,methyl green or Victoria blue BSA.

In addition to the photosensitive dye or dyes and the compound offormula (I), such a composition can also contain a cosmetic film-formingresin, a foaming agent, perfume and other such cosmetic adjuvants.

Representative cosmetic film-forming resins are those having generally amolecular weight ranging from 10,000-700,000 or even higher.Representative cosmetic film-forming agents that can be employed,generally in amounts of 0.5-5 weight percent includepolyvinylpyrrolidone having a molecular weight of about 10,000 to700,000, copolymer of vinylpyrrolidine/vinyl acetate, 70%/30% to 30%/70%having a molecular weight of 40,000-400,000, copolymer of vinyl acetateand an unsaturated carboxylic acid such as a copolymer containing 90%vinyl acetate and 10% crotonic acid having a molecular weight of 45,000to 70,000; terpolymer of methyl methacrylate (15-25%)/stearylmethacrylate (18-28%) and dimethyl methacrylate (52-62%), andparticularly in the proportions of 20%/23%/57%, respectively, and vinylacetate (75-85%)/allyl stearate (10-20%)/allyloxyacetic acid (3-10%)terpolymer, particularly in proportions of 80%/15%/5%, respectively,copolymer of maleic anhydride and methylvinylether in a molar ratio ofpreferably 1:1 and having a specific viscosity between 0.1-3.5 whenmeasured at 25° C. and at a concentration of 1 g in 100 cc ofmethylethyl ketone, and the monoethylester, monoisopropylester ofmonobutylester of said maleic anhydride, methyl vinyl ether copolymerand copolymer of maleic anhydride and butyl vinyl ether.

Representative examples of cosmetic compositions containing a compoundof formula (I) either to protect the photosensitive dye contained in thecomposition or to avoid their yellowing, include capillary compositionssuch as hair lacquers, plastifying hair setting lotions, hair treatingor disentangling setting lotions, shampoos, dye shampoos, hair dyecompositions, fingernail polishes, skin treating creams and basemakeups. These compositions can thus be packaged and stored without anyrisk of alteration, in transparent glass or plastic containers.

Further, the compositions of the present invention can also be providedin the form of an aerosol and be packaged under pressure in an aerosolcontainer together with one or more conventional aerosol propellantssuch as those known as "Freon" and particularly dichlorodifluoromethane,trichloromonofluoromethane and mixtures thereof.

The present invention also has for an object a process for protectingcosmetic compositions capable of being altered or degraded by light rayswhich comprises incorporating into these compositions at least onecompound of formula (I) in an amount of 0.05 to 5% by weight of saidcomposition.

The following non-limiting examples in which the percentages unlessotherwise indicated are by weight will give a better understanding ofthe present invention.

EXAMPLES OF PREPARATION EXAMPLE 1: Preparation of 4-(2-oxo-3-bornylidenemethyl) benzene sulfonic acid

120 g of benzylidene camphor (0.5 mole) are added with stirring to 320ml of oleum containing 20% SO₃, the rate of addition being regulated sothat the temperature does not exceed 50° C. The stirring is continuedfor an hour at ambient temperature. The reaction mixture is then slowlypoured into 200 ml of ice water and the above sulfonic acid precipitateson cooling. After allowing to stand for several hours at 0° C., theprecipitate is filtered, then dissolved in 50 ml of water andreprecipitated by addition of 25 ml of concentrated hydrochloric acid.After filtering and drying in a dessicator in the presence of potash,104 g of a white powder melting at 100° C. are obtained. This productcontains 1.5 moles of crystallization water.

When left in air, the product fixes an additional 1.5 moles of water,the resulting compound thus obtained having the formula C₁₇ H₂₀ SO₄.3H₂O and the following characteristics:

Mol. weight=374, Acid value=2.68 meq/g, Theory 2.67 meq(Milliequivalent/g)

    ______________________________________                                        Elementary analysis:                                                                    Calculated %                                                                            C: 54.54 H: 6.95 S: 8.55                                            Found %   54.79    6.84    8.65                                     ______________________________________                                    

EXAMPLE 2: Preparation of sodium 4-(2-oxo-3-bornylidene methyl) benzenesulfonate

To a solution of 50 g of acid prepared according to example 1, in 100 mlof water, there are added 7.1 g of anhydrous sodium carbonate. Theprecipitate obtained is filtered and recrystallized in an 80:20water-acetone mixture. There are obtained 43 g of white flakes having amelting point of 240° C.

After prolonged drying on phosphoric anhydride, a determination of waterindicates the presence of 2 moles of crystallization water. When left inthe air, the salt fixes one additional mole of crystallization water.

EXAMPLE 3: Preparation of magnesium 4-(2-oxo-3-bornylidene methyl)benzene sulfonate of the formula ##STR5##

The reaction mixture obtained by reacting 12 g of benzylidene camphorand 32 ml of oleum with 20% SO₃ in accordance with the proceduresoutlined in example 1 is poured into a saturated magnesium chloridesolution. After crystallization in a mixture of water and acetone, 7.3 gof white-beige flakes, melting at a temperature above 360° C., arecollected.

A determination of water indicates the presence of 8 moles ofcrystallization water.

Of course, in the case of a metal with "n" valence in place ofmagnesium, the developed formula would comprise "n" radicals of[4-(2-oxo 3-bornylidene methyl) benzene sulfonate].

EXAMPLE 4: Preparation of calcium 4-(2-oxo-3-bornylidene methyl) benzenesulfonate

Calcium hydroxide is added, until a basic pH is reached, to a solutioncontaining 7.48 g of acid prepared according to example 1 in 15 ml ofwater. The precipitate is filtered and recrystallized in 80 ml of water.Thus, 5.8 g of a whitish crystalline powder, retaining 5 moles of waterper mole of sulfonate, and having a melting point above 360° C., areobtained.

EXAMPLE 5: Preparation of 4-(2-oxo-3-bornylidene methyl) benzenesulfonate of bis-(2-hydroxy ethyl) ammonium

While stirring, 1.05 g of diethanolamine are added to an aqueoussolution (10 ml) of 3.74 g of the acid prepared according to Example 1.After evaporation to dryness, a light yellow powder, melting at 85° C.,is obtained. The salt obtained retains a mole of water and has theempirical formula

    ______________________________________                                        Elementary analysis:                                                          Calculated %    C: 56.86 H: 7.50 N: 3.16                                                                             S: 7.23                                Found %         56.48    7.38    3.08  7.51                                   ______________________________________                                    

EXAMPLE 6: Preparation of sodium 2-methyl-5-(2-oxo-3-bornylidene methyl)benzene sulfonate

25.4 g of 3-p-tolylidene camphor are added to 64 ml of oleum containing10% SO₃, with cooling so as to keep the temperature of the reactionmixture around 35° C. The resulting mixture is then poured into 150 mlof a saturated sodium chloride solution, the mixture being cooled tobelow 25° C. A precipitate is obtained which is filtered and then washedwith a saturated sodium chloride solution. The wet product is made intopaste in 70 ml of water. It is then filtered and recrystallized in an80:20 water-acetone mixture. Thus, 29.3 g of a white powder, melting at240° C. are obtained.

After drying in a dessicator on phosphoric anhydride, a determination ofwater indicates the presence of 2 moles of crystallization water.

EXAMPLE 7: Preparation of 2-methyl 5(-2-oxo-3-bornylidene methyl)benzene sulfonic acid

To 8.65 g of sodium salt, prepared according to Example 6 and dissolvedin 125 ml of water, there are added 62.5 ml of concentrated hydrochloricacid. The precipitate obtained is filtered and dried on potash to obtain8 g of white powder.

This product, crystallized with two moles of water, melts at 130° C. Ithas the formula C₁₈ H₂₂ SO₄.2 H₂ O and a molecular weight of 370.

Acid value: 2.63 meq/g, (theory: 2.64 meq/g)

    ______________________________________                                        Elementary analysis:                                                                    Calculated %                                                                            C: 58.38 H: 7.03 S: 8.65                                            Found %   58.38    6.84    8.62                                     ______________________________________                                    

Example 8: Preparation of sodium 3-benzylidene-2-oxo-10-bornanesulfonate

A mixture of 37 g of anhydrous camphosulfonic acid and 173 g of sodiummethylate in 600 ml of toluene is heated for 1 hour at reflux withstirring. After cooling to ambient temperature, 16.95 g of benzaldehydeare added with stirring. The resulting mixture is heated for 3 hours atreflux and then cooled to ambient temperature at which time there areadded thereto 150 ml of water with good stirring. The resultingprecipitate is filtered, dried, and then recrystallized in 200 ml ofwater to obtain, after drying in a dessicator, white flakes (40.55 g)melting at 230° C.

The sodium salt thus obtained contains 0.5 mole of water per mole. Whenleft in the air, it stabilizes after having fixed about 3 moles ofcrystallization water.

Example 9: Preparation of 3-benzylidene-2-oxo-10-bornane sulfonic acid

20 g of the sodium salt of Example 8 are dissolved with heating in 200ml of water. 100 ml of concentrated hydrochloric acid are then addedwith stirring. The precipitate obtained is filtered and dried in adessicator in the presence of potash and phosphoric anhydride. Thus,15.3 g of a white powder, melting at 124° C., are obtained. This productcontains a mole of crystallization water.

Acid value: (theory: 2.96 meq/g); found 2.95 meq/g

When left in air, this compound fixes another mole of water to give theempirical formula: C₁₇ H₂₀ O₄ S.2 H₂ O; (molecular weight: 356).

Acid value: 2.82 meq/g; theory: 2.81 meq/g

    ______________________________________                                        Elementary analysis:                                                                    Calculated %                                                                            C: 57.30 H: 6.74 S: 9.07                                            Found %   57.02    6.62    8.99                                     ______________________________________                                    

Example 10: Preparation of sodium 2-chloro-5-(2-oxo-3-bornylidenemethyl) benzene sulfonate

There are added, by portions, 274.5 g of 3-p-chlorobenzylidene camphorto 1000 ml of oleum containing 20% by weight of SO₃, while maintainingthe well stirred mixture at a temperature below 50° C. When the additionhas been completed, the resulting reaction mixture is poured into 3liters of a saturated solution of sodium chloride, while cooling thesame. The precipitate formed is filtered and washed with a saturatedsolution of sodium chloride, then with a little cold water. There arethus obtained 215 g of a whitish powder melting at 260° C.

Determination of water, by the Fischer method, indicates the presence of3 moles of crystallization water.

Example 11: Preparation of 2-chloro-5-(2-oxo-3-bornylidene methyl)benzene sulfonic acid

The salt produced in Example 10 is treated in accordance with theprocedures described in Example 7. An oil, which crystallizes slowly, isobtained.

The product thus produced (yield=90%) melts at 140° C. The acid valueand determination of water by the Fischer method indicate the presenceof 4 moles of crystallization water.

Acid value: Calculated 2.35 meq/g. Found 2.36.

Water: Calculated % 16.9. Found % 16.9.

Example 12: Preparation of 4-chloro-(2-oxo-3-bornylidene methyl) benzenesulfonate of 1,1-bis(hydroxymethyl) ethylammonium

The procedures outlined in Example 5 are followed except that thediethanolamine is replaced by 2-amino-2-methyl propane-1,3-diol. Thereis thus obtained a white powder, melting at 145° C., the solubility ofwhich is 17% by weight in water and 33% by weight in ethanol at 50° C.Elementary analysis: C₂₁ H₃₁ NO₆ S

    ______________________________________                                        Calculated %                                                                              C: 59.29  H: 7.29  N: 3.29                                                                              S: 7.53                                 Found %     59.33     7.04     3.38   7.62                                    ______________________________________                                    

Example 13: Preparation of sodium 3-p-tolylidene-2-oxo-10-bornanesulfonate

The procedures outlined in Example 8 are repeated except that thebenzaldehyde is replaced by p-tolualdehyde.

The above product is obtained in the form of light yellow crystals(yield 74%), melting at 190° C. Analysis indicates the presence of 3.5moles of crystallization water.

Example 14: Preparation of 3-p-tolylidene-2-oxo-10-bornane sulfonic acid

The sodium 3-p-tolylidene-2-oxo-10-bornane sulfonate produced in Example13 is treated in accordance with the procedures outlined in Example 9.The product obtained contains 1 mole of crystallization water and meltsat 220° C.

Acid value: Calculated 2.82 meq/g. Found 2.82 meq/g.

Elementary analysis=C₁₈ H₂₄ O₄ S.H₂ O

    ______________________________________                                        Calculated %                                                                              C: 61.36   H: 6.82   S: 9.09                                      Found %     61.76      6.83      9.11                                         ______________________________________                                    

Example 15: Preparation of 4-methyl-5-(2-oxo-3-bornylidene methyl)benzene sulfonic acid having the formula ##STR6##

25.4 g of 3-o-methylbenzylidene camphor are dissolved with stirring in84 ml of oleum containing 20% by weight SO₃ with cooling so as tomaintain the temperature below 25° C. Stirring of the resulting reactionmixture is continued for an additional 30 minutes at ambient temperatureat which time it is poured into 200 ml of crushed ice. The precipitatewhich forms is filtered and crystallized in 100 ml of acetone to producewhite crystals melting at 130° C. and corresponding to the dihydrate.

Acid index: Calculated 2.70 meq/g. Found 2.74 meq/g.

Elementary analysis: C₁₈ H₂₂ O₄ S.2H₂ O

    ______________________________________                                        Calculated, %                                                                             C: 58.38   H: 7.03   S: 8.65                                      Found, %    58.36      6.97      8.46                                         ______________________________________                                    

Example 16: Preparation of zinc 4-(2-oxo-3-bornylidene methyl) benzenesulfonate of the formula ##STR7##

37.4 L g of 4-(2-oxo-3-bornylidene methyl) benzene sulfonic acidtrihydrate and 6.3 g of zinc carbonate are heated in 250 ml of wateruntil dissolution occurs. The resulting solution is then filtered. Theabove zinc salt which precipitates on cooling is filtered and thencrystallized in 400 ml of water. 64.5 g of white crystals are recovered,melting at 250° C.

Determination of water by the Fischer method reveals the presence of9.5% water, i.e. 4 moles of crystallization water.

Acid index: Calculated 2.57 meq/g. Found 2.54 meq/g.

Example 17: Preparation of B 4-(2-oxo-3-bornylidene methyl) benzenesulfonate of 4-amino-4-carboxyl butyl guanidinium

18.7 g of 4-(2-oxo-3-bornylidene methyl) benzene sulfonic acid and 8.7 gof arginine are dissolved in water (75 ml). The resulting solution isevaporated to dryness under a vacuum. The residue is ground in a littlesulfuric ether and then filtered, yielding thus 25.6 g of a whitishpowder melting at 265° C.

Amine Index: Calculated 2.03 meq/g. Found 2.05 meq/g.

Elenentary Analysis: C₂₃ H₃₄ N₄ O₆ S

    ______________________________________                                        Calculated, %                                                                              N: 11.33     S: 6.48                                             Found, %     11.10        6.55                                                ______________________________________                                    

EXAMPLES OF COMPOSITIONS

The compounds of formula (I) can be incorporated directly either in acomposition for protecting human skin against solar radiations or in acomposition containing components sensitive to light. When the compoundsof formula (I) are in the form of sulfonic acids, i.e. with R and/or R'being equal to SO₃ H, they can easily be neutralized to the desired pHwith an organic or inorganic base, selected as a function of itsparticular cosmetic properties and the desired solubility of theresulting compound.

ANTISOLAR COMPOSITIONS

Example A--An antisolar lotion is prepared by admixing the followingcomponents:

Lanolin--2.5 g

Butylhydroxyanisole--0.025 g

Butylhydroxytoluene--0.025 g

Octyl gallate--0.0125 g

Triglycerides of fatty acids having 8-12 carbon atoms--40 g

Perfume--1.25 g

3-benzylidene-2-oxo-10-bornane sulfonic acid--4 g

Ethyl alcohol, 96° titer, q.s.p.--100 g

Example B--An antisolar lotion is prepared by admixing the followingcomponents:

Glycerin--5 g

Polyethylene glycol (MW=400)--0.5 g

Ethoxylated lanolin--1 g

Soluble perfume--2 g

Sodium 2-methyl-5-(2-oxo-3-bornylidene methyl) sulfonic acid--2g

Ethyl alcohol, 96° titer--50 g

Water, q.s.p.--100 g

Example C--An antisolar aerosol spray is prepared by admixing thefollowing components and packaging the same under pressure in an aerosolcontainer:

Absolute ethyl alcohol--30 g

Isopropyl myristate--20 g

Castor oil--2 g

Lanolin--5 g

Perfume--B 1 g

Magnesium-4-(2-oxo-3-bornylidene methyl) benzene sulfonate--2 g

Dichlorodifluoromethane--40 g

Example D--An antisolar aerosol foam is prepared by admixing thefollowing components and packaging the same under pressure in an aerosolcontainer:

Sipol wax--3.5 g

Vaseline oil--B 6 g

Isopropyl myristate--3 g

Preservative--"Nipa ester 82521" (mixture of methyl, ethyl, butyl andbenzyl esters of hydroxy benzoic acid)--0.3 g

Glycerin--10 g

Perfume--0.3 g

4-(2-oxo-3-bornylidene methyl) benzene sulfonate of(1,3-dihydroxy-2-methyl-2-propyl) ammonium--2.5 g

Water, q.s.p.--100 g

To make the aerosol, 87 g of the solution prepared above are admixedwith 13 g of dichlorodifluoromethane.

Example E--An antisolar cream is prepared by admixing the followingcomponents:

Cetylstearyl alcohol--2 g

Glycerol monostearate--4 L g

Cetyl alcohol--4 g

Vaseline oil--5 g

Butyl stearate--5 g

Propylene glycol (MW=400)--7 g

Silicone oil--0.125 g

Ethylene oxide polymer having a molecular weight of100,000--1,000,000--sold under the tradename "Polyox" (0.5%)--3.5 g

Preservative--"Nipa ester 82521" as in Example D--0.3 g

Perfume--0.4 g

4-(2-oxo-3-bornylidene methyl) benzene sulfonate of bis(2-hydroxy ethyl)ammonium--4 g

Water, q.s.p.--100 g

Example F--An antisolar milk is prepared by admixing the followingcomponents:

Sipol wax--5 g

Vaseline oil--6 g

Isopropyl myristate--3 g

Silicone oil--1 g

Cetyl alcohol--1 g

Glycerin--20 g

Preservative--"Nipa ester 82521" as in Example D--0.3 g

Perfume--0.3 g

2-methyl-5-(2-oxo-3-bornylidene methyl) benzene sulfonate of(1,3-dihydroxy-2-methyl-2-propyl) ammonium--3 g

Water, q.s.p.--100 g

PRESERVATION OF COLORED PRODUCTS

Example G--A colored hair setting lotion for live human hair is preparedby admixing the following components:

4-(2-oxo-3-bornylidene methyl) benzene sulfonic acid--0.2 g

Vinylpyrrolidone-vinyl acetate copolymer, 70%/30% MW=40,000--2 g

Victoria blue BSA dye, C.I. 44045--0.001 g

Ethyl alcohol--50 g

Triethanolamine, q.s.p. pH 7

Water, q.s.p.--100 ml

Example H--A colored setting lotion is prepared by admixing thefollowing components:

2-methyl-5-(2-oxo-3-bornylidene methyl) benzene sulfonic acid--0.2 g

Crotonic acid-vinyl acetate copolymer 10%/90%, MW=50,000 having aviscosity of 7-9 cps at 35° C. in a 5% solution of tetrachloroethane--2g

C.I. Basic Violet No. 3, C.I. 42555--0.01 g

Ethyl alcohol--50 g

Triisopropanolamine, q.s.p. pH 7

Water, q.s.p.--100 ml

Example I--A colored setting lotion is prepared by admixing thefollowing components:

2-methyl 5(2-oxo-3-bornylidene methyl) benzene sulfonic acid--1.5 g

Polyvinyl pyrrolidone K 30--3 g

methyl violet C. I. 42535--0.005 g

Ethyl alcohol--20.0 g

Triethanolamine q.s.p.--pH 8

Water q.s.p.--100 cc

What is claimed is:
 1. A process for the preparation of4-(2-oxo-3-bornylidene methyl) benzene sulfonic acid comprising reactingbenzylidene camphor with oleum at a temperature not exceeding 50° C. andthereafter cooling the reaction mixture so as to precipitate theresulting sulfonic acid.
 2. The process of claim 1, which furtherincludes the step of treating the reaction mixture, after reaction withan effective amount of Na₂ CO₃ so as to precipitate the sodium salt ofthe said sulfonic acid.
 3. The process of claim 1, which includes thefurther step of reacting the reaction mixture, after reaction, with aneffective amount of a saturated solution of magnesium chloride so as toproduce the magnesium salt of said sulfonic acid.
 4. The process ofclaim 1, which includes the additional step of reacting the reactionmixture, after reaction, with a stoichiometrical amount ofdiethanolamine to produce the bis-(2-hydroxy ethyl) ammonium salt ofsaid sulfonic acid.
 5. The process of claim 1 which includes theadditional step of reacting the reaction mixture, after reaction, withan effective amount of arginine to produce the 4-amino-4-carboxy butylguanidinium salt of said sulfonic acid.
 6. A process for the preparationof a compound of the formula ##STR8## wherein R is alkyl having 1-4carbon atoms or halogen comprising reacting a compound of the formula##STR9## wherein R has the meaning given above with oleum, maintainingthe reaction temperature at about 35° C.-50° C. and precipitating thesodium salt of the resulting sulfonic acid by the addition of asaturated sodium chloride solution at a temperature below 25° C.
 7. Aprocess for the preparation of a compound of the formula ##STR10##wherein R is alkyl having 1-4 carbon atoms or halogen comprisingreacting the compound obtained in accordance with claim 6 withconcentrated hydrochloric acid.
 8. A process for the preparation of4-methyl-5-(2-oxo-3-bornylidene methyl) benzene sulfonic acid comprisingreacting 3-o-methyl benzylidene camphor with oleum.